CN101128503A - Two-component epoxy adhesive composition - Google Patents
Two-component epoxy adhesive composition Download PDFInfo
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- CN101128503A CN101128503A CNA2006800063381A CN200680006338A CN101128503A CN 101128503 A CN101128503 A CN 101128503A CN A2006800063381 A CNA2006800063381 A CN A2006800063381A CN 200680006338 A CN200680006338 A CN 200680006338A CN 101128503 A CN101128503 A CN 101128503A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
The present invention relates to a two-component epoxy adhesive composition comprising a) a first component comprising a first epoxy resin and a second epoxy resin, the second epoxy resin being flexibilized by an elastomer, and b) a second component comprising at least one amine compound with one or more primary and/or secondary amino groups, said amine compound having a molecular weight of less than 450 g/mol. The ratio of the total number of amino groups of the amine compound to the total number of epoxy groups of the epoxy resins is 0.01:1 to 0.5:1. The mixing of the two components a) and b) results in a wash-off resistant composition. Said wash-off resistant composition results upon heat-curing in a crash-stable structural adhesive.
Description
The present invention relates to two-component epoxy adhesive composition, by mixing two kinds of obtainable washable decyclization epoxy resins binder compositions of component, the method for utilizing at least two faces of epoxy adhesive composition general or parts to couple together.The invention further relates to the application of two-component epoxy adhesive composition, it is used for oiliness metallic surface and vehicle part are connected to become the stable assembly of collision.The present invention also relates to the application of amine compound in epoxy resin binder as reagent.
Epoxy adhesive composition is the reactive binder composition that contains Resins, epoxy, solidifying agent and common potential promotor.During heating, the epoxide group of Resins, epoxy and solidifying agent reaction connect epoxy resin compound by adding into reaction, obtain the solidified product.
This solidifying product has good mechanical property and erosion resistance, is better than the solidifying product of other reactive adhesive.It is particularly useful that these characteristics make the epoxy tackiness agent press for satisfied field in the machinery requirement, for example, and in the automotive industry.For example connect, vehicle comprises that the tackiness agent of body construction parts such as automobile, truck (lorry), bus or train is called as construction adhesive.
In general, heat-setting epoxy resin binder is used as construction adhesive.
In vehicle was made, the thermal curable construction adhesive that has been used for body in white (body-in-white) structure was easy to hydro-peening or adopts other purging method, carried out phosphatization and electrophoretic painting before final this construction adhesive of thermofixation in the electrophoresis stove.In order to prevent that the thermal curable construction adhesive from being washed off, carry out Procuring by heat treating method traditionally, as induction Procuring or the Procuring of use body in white baker (case).Yet this extra pre-cure step makes the course of processing complicated.In addition, the body in white baker is also very expensive.
As a selection of thermal curable epoxy resin binder, considered to use bicomponent epoxy adhesive as construction adhesive.Bicomponent epoxy adhesive comprises two kinds of independently components, and first kind of component comprises Resins, epoxy, and second kind of component comprises the epoxide-reactive compound.This bicomponent epoxy adhesive generally solidifies after two components are mixed immediately, does not need the thermal curable epoxy resin binder to carry out Procuring and solidified device.
Many bicomponent epoxy adhesives had been put down in writing in the past.
US-B-4,728,737 disclose the two-component structure adhesive (proposing as a reference) that comprises epoxy resin ingredient and hardener component here.
US-B-4,916,187 relate to the epoxy resin binder that the two-pack by first kind of polyepoxide component and second kind of curing component constitutes, and the latter is included in finely disseminated polyamine and polyphenol solid salt (proposing as a reference) in the liquid adducts here.
US-B-5,629,380 disclose the bicomponent epoxy adhesive that comprises first kind of component and second kind of component, and the former comprises epoxy resin catalyst and ammonia solidifying agent, and the latter comprises functionality greater than 1 Resins, epoxy (proposing as a reference) here.
US 2002/0164485 and US-B-6,577,971 all relate to the two-component epoxy adhesive composition that comprises first kind of component and second kind of component, and the former comprises Resins, epoxy and silane coupling agent, and the latter comprises aliphatic amide and polyamine (proposing as a reference) here.
US-B-6,248,204 disclose the curable epoxy resin at room temperature tackiness agent that comprises first kind of component and second kind of component, and the former comprises Resins, epoxy, and the latter comprises the solidifying agent (proposing as a reference) of ammonia here.
Yet there are several shortcomings in above-mentioned tackiness agent, has limited its application as construction adhesive.Begin immediately to solidify because component is mixed under the room temperature of back, make its working life very short, just component can use the time of epoxy resin binder very short after mixing.Therefore, used epoxy resin binder after, the assembling of interconnecting piece to carry out immediately.In addition, the solidifying product of described two-component epoxy adhesive composition formation generally can not satisfy the requirement as construction adhesive.Particularly, the collision stability of described bicomponent epoxy adhesive solidifying product can not satisfy an urgent demand that this respect is used.In general, the second-order transition temperature of solidified bicomponent epoxy adhesive is low.Its oil absorbency is poor, makes its very unfavorable of seeming in needs will be stained with the automobile industry that couples together of steel of oil.
The purpose of this invention is to provide need not hot Procuring wash-resistant two-component structure adhesive, it has the built-up time of several hrs, can under its uncured state, store several weeks, can obtain having high collision stability, high glass-transition temperature and the good solidifying product of oil absorbency.
This purpose can be obtained by bicomponent epoxy adhesive, and this bicomponent epoxy adhesive comprises:
A) comprise first kind of component of first Resins, epoxy and second Resins, epoxy, second Resins, epoxy by elastic body toughening and
B) comprise second kind of component of at least a amine compound, this amine compound have one or more uncle's ammonia and (or) the parahelium group, described amine compound has the molecular weight less than about 450g/mol,
Wherein, the ratio of the amine groups sum of amine compound and the epoxide group sum of Resins, epoxy is between about 0.01: 1 to about 0.5: 1, two kinds of components a) and b) mix and obtained the washable binder composition that goes, the described washable construction adhesive that goes binder composition to form collision stable (crash-stable) by thermofixation.
Components b) the amine compound agent effect that reacts in, it causes forming washable going property.Because the reaction of Resins, epoxy and amine compound, after two kinds of components were mixed, the viscosity of epoxy adhesive composition was from less than about 1, and 000Pas is increased at least about 2, the nearly constant plateau value of 000Pas (23 ℃ equal 0.01 condition under with shearing rate).The binder composition of this pre-reaction, just high than single component viscosity not completely solidified binder composition has washable going property.Therefore, spatter when use and wash or during other purging method, the epoxy adhesive composition that is used for the body in white structure can't is washed off.
Be mixed to washable changing to about 24 hours scope at about 30 minutes during this period of time of going to form from two kinds of components, this depends on the amount of amine compound in the binder composition.Like this, by selecting the appropriate amount of amine compound in the binder composition, can cause the later formation of washable going property.Use latter two adhesive face of epoxy resin binder to be sticked together for a long time, make the actual assembled between remote manipulation point and the use of tackiness agent become possibility.
Fig. 1 is the curve of formula A5/B5 medium viscosity to the time.
Fig. 2 is the curve of formula A3/B2 medium viscosity to the time.
Fig. 3 is the curve of formula A4/B4 medium viscosity to the time.
Fig. 4 is formula A3/B2 medium viscosity and the yielding stress curve to the time.
Fig. 5 is formula A4/B4 medium viscosity and the yielding stress curve to the time.
Fig. 6 be among the formula A3/B2 stretching lap shear strength and stripping strength to the curve of time.
Fig. 7 be among the formula A2/B1 stretching lap shear strength and stripping strength to the curve of time.
When the epobond epoxyn that uses is washable go performance to form after, just remain on the state of pre-reaction. Pre-reaction epoxy adhesive composition of the present invention shows low-down moisture sensitivity. Under 23 ℃ and 50% relative humidity, can keep reaching the open hour in about 4 weeks.
What can select is, accelerates or improves pre-reaction such as precuring methods such as induction precuring methods.
In order to obtain to have the cured article of desired properties, epoxy adhesive composition will carry out last curing schedule, is about to it and is heated at least about more than 120 ℃, preferably keeps ten minutes preferably at least two ten minutes more than 140 ℃ at least. Demonstrate all properties of outstanding construction adhesive after the final curing of epoxy adhesive composition of the present invention. Particularly compare with traditional bicomponent epoxy adhesive, its stretching lap shear strength and peel strength are higher. Therefore, the collision stability of epobond epoxyn of the present invention is improved widely.
In preferred scheme, according to the cold-rolled steel of ISO 11343 at 1mm, as testing on the 1403 type cold-rolled steels, the peel strength of cure adhesive on iron and steel is at least about 20N/mm or stronger, better between the about 50N/mm of about 25-.
Its glass transition temperature is higher than 80 ℃. In addition, with traditional bicomponent epoxy adhesive comparison, epoxy adhesive composition of the present invention has better oil absorption. This seems in needs will be stained with the vehicle manufacturing that couples together of metal surface of oil and is even more important. When in the end heating epobond epoxyn in the curing schedule, adhesive is softening, effectively sops up and remains in lip-deep oil to be connected. More optimizedly, the first ring epoxy resins is hard epoxy. Used epoxy resin is the epoxy resin that comprises group shown in the following molecular formula in the compound of the present invention
Wherein, R8Be H or C1-4Alkyl, preferred H or methyl most preferably are H. Here used hard epoxy (rigid epoxy resin) refers to contain the epoxy resin of bis-phenol part in epoxy backbone. The representative product of preferred useful bisphenol resin refers to U.S. 5,308 among the present invention, and the 8th row, the disclosed part of the 6th row are given by formula 6 in 895. Relevant portion in this patent is incorporated by reference here. Preferably, hard epoxy is the mixture that liquid-state epoxy resin or solid epoxy resin are dispersed in liquid-state epoxy resin. The hard epoxy that override is selected is bis-phenol and bisphenol-f A type resin. The preferred liquid-state epoxy resin of first ring epoxy resins is such as D.E.RTM330 and D.E.RTM331 bisphenol A epoxide resins (from Dow Chemical) or solid epoxy are such as bisphenol A epoxide resin D.E.RTM671 (from Dow Chemicals), or its mixture.
Second Resins, epoxy is generally finished by known toughening technology, as EP-A-1, and 359,202 and the described technology of U.S.2005/159511 (for reference herein).For example, can be by the toughness reinforcing Resins, epoxy of acrylonitrile butadiene copolymer, as STRUKTOL
TM3604 (from Schill+Seilacher companies).
The amine compound that contains one or more uncle's ammonia and/or parahelium group is selected from fat or cycloaliphatic diamines or polyamine, and it comprises polyether diamine and polyamine and polyimide.In preferred scheme, amine compound is selected from and comprises 4,7,10-three oxygen tridecyls-1, and the 13-diamines, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, aminoethyl piperazine and polytrimethylene ether diamines and polytrimethylene ether triamine are as JEFFAMINE
TMPolyethers polyamine type (from Huntsman company).
In a further preferred embodiment, first and second components equal 0.01 o'clock viscosity less than 1 23 ℃ and shearing rate, 000Pas, make two kinds of components can be easy to mix like this, epoxy adhesive composition can be used for substrate by traditional method, as utilizes robot bead application (bead application) or applied by hand to take out chuck (CARTRIDGE).
Especially, two components a) and b) at least one contain toughner.More preferably, toughner is selected from the compound shown in the formula I
Wherein, m equals 1 or 2, and n is 2 to 6, R
1For removing the n valency group of elasticity prepolymer behind isonitrile acid fat, amino or the hydroxyl, elasticity prepolymer solubilized or be scattered in the Resins, epoxy, W and X be respectively-O-or-NR
3-, at least one is-NR among W and the X
3-, R
2For after removing phenolic hydroxyl group and optionally removing amino group, the m+1 valency group of poly-phenol or ammonia phenol, R
3Be H, C
1-C
6Alkyl chain or phenol, and the compound shown in the formula II
Wherein, p equals 1 or 2, and q is 2-6, and Y is-O-,-S-, or-NR
6-, and Z is for being selected from-OH-NHR
6,-OCN group,
R
4Be the stub of fragment polyethers, polythioester or the polyamine of the stub of hydroxyl, sulfydryl or amino terminated polyether prepolymer or hydroxyl, sulfydryl or amino end capped prepolymer, R
5For the Z group directly is connected in the aromatic carbocyclic on the aromatic nucleus or the p+1 valency group of aromatic hydrocarbon (araliphatic), R
6Be H, C
1-C
6Alkyl or phenyl, and R
7Be methyl or H.Said composition can comprise the mixture of toughner shown in toughner shown in the formula I and the formula II.
Toughner shown in the formula I is at EP-A-0,308,664 (page 5 14 walks to the 13rd page of 24 row) and U.S.5,278,257 (the 2nd hurdle 14 walks to 32 row, the 4th hurdle 19 to 31 row, and the 4th hurdle 57 row, go in the 16th hurdle 18, embodiment 1-6, the 20th hurdle 40 walk to 68 the row) in provided detailed description, for reference herein.Toughner shown in the formula II is at EP-A-0,353,190 (page 3 51 walks to the 6th page of 62 row), (U.S.5,073,601, the 1st hurdle 59 walks to the 2nd hurdle 16 row, and the 3rd hurdle 60 walks to the 9th hurdle 21 row and U.S.2005/0760634 0014 to 0053 section) in provided detailed description, for reference herein.The example of toughner is FLEXIBILIZER
TMDY 965 (embodiment 13 described preparations among the reference EP 308,664) and DY 3333 (with reference to the document U.S.2005/070634 that is provided, 0074 to 0075 section described toughner B).Other example of toughner is International Patent Application WO 2005/007766 (with reference to 0072 to 0073 and 0076 to 0077 section of document U.S.2005/070634 provided here) described toughner A and toughner B.
In preferred embodiments, the elastomerics that is used for toughness reinforcing second Resins, epoxy is an acrylonitrile-butadiene rubber.
In the embodiment of further optimizing, two kinds of components a) and b) at least a component comprise latent stiffening agent, its consumption is less than 10% of composition total weight.Latent stiffening agent is meant under the room temperature and does not react, and the compound that after temperature raises, reacts as solidifying agent.The preferred stiffening agent of diving is described in the EP 197,892 (reference U.S.4,659,779 the 4th hurdles 17 walk to 34 row and U.S. Patent application 2005/070,634 62 sections) herein.Most preferred stiffening agent is a dicyanamide.
Further in the preferred version, components b) comprises hydrophobic diluents.The boiling point of hydrophobic diluents preferably is at least more than 220 ℃ at least more than 200 ℃, preferably at least more than 250 ℃.So allow further to adjust on request components b) viscosity.
Preferably, hydrophobic diluents is a hydrocarbon material.Especially at room temperature (23 ℃) are liquid.Aromatic alkyl chain substituted aromatics more preferably, the naphthalene that replaces as alkyl.Preferred thinner is diisopropylnaphthalene and triisopropyl naphthalene.
Preferably, two kinds of components a) and b) at least a component comprise one or more additives, it is selected from dive promotor, adhesion promotor, epoxy silane, pyrogenic silica, wetting agent and mineral filler, as calcium oxide, lime carbonate, wollastonite or talcum.
In further preferred version, two kinds of components a) and b) at least a component contain at least a uncle's list or polyamine or their mixture as promotor." polyamine (polyamine) " comprises diamines.Because the reason of promotor, initial wet tenacity (initial green strength) promptly greater than the intensity of 0.2MPa, can be mixed the back two kinds of components and form in a few hours.Preferred amine promoter walks to 32 and U.S.2005/070 15 page 29 of WO 2005/07,766, described (proposing for reference here) is arranged in the 65th section of 634.An example of this promotor is 2,4,6-three (dimethylamino methyl) phenol.
If list or polyamine be included in component a) in, will be embedded in the polymeric matrix like that as EP 197,892 (U.S.4,659,779 the 2nd hurdles 39 walk to 57 row and the 4th hurdle 34 walks to the 6th hurdle 51 row, and are for reference herein) is disclosed.
An example of this embedding polyamine is European patent No.EP-B-0,197,892 disclosed EP 796 (reference herein is U.S.4,659,779).
According to preferred embodiment, first component a) and second components b) weight ratio between 2: 1 to 10: 1, the ratio of the amine groups sum of amine compound and the epoxide group sum of Resins, epoxy is between 0.06: 1 to 0.2: 1.
In this embodiment, preferably:
A) first component comprises the about 80 weight % of about 30 weight %-first Resins, epoxy, second Resins, epoxy of the about 30 weight % of about 5 weight %-and about 20 weight % or less than the toughner of 20 weight %,
B) second component comprises the amine compound of the about 40 weight % of about 1 weight %-, the toughner of the about 80 weight % of about 10 weight %-and the hydrophobic diluents of about 10 weight %-30 weight %,
Two kinds of components a) and b) at least a component comprise mineral filler, epoxy silane, wetting agent, pyrogenic silica, the stiffening agent of diving, dive promotor or their mixture.
Owing to have very high oil absorbency, bicomponent epoxy adhesive of the present invention is specially adapted to connect the butyrous metallic surface.
Be particularly useful for connecting vehicle parts such as parts, just as construction adhesive as automobile, lorry, truck (lorry), bus and train.Also can be used for fabricated ship and aircraft components.
The present invention and then relate to washable decyclization epoxy resins tackiness agent, its first component by mixing above-mentioned two-component epoxy adhesive composition a) and second components b) obtain.Blend compositions is through about 1 hour to several days, and the abundant Procuring after preferably about 1 hour to 24 forms the washable characteristic of going.Combine with substrate immediately after premixed tackiness agent preferably mixes, especially do not surpass 20 minutes, preferably not above 10 minutes.
The present invention also relates to utilize mix above-mentioned two-component epoxy adhesive composition first component a) and second components b) obtain washable decyclization epoxy resins binder composition, and the mixture that obtains by heat treating method Procuring.
In the process that connects isolating surface, the component of above-mentioned two-component epoxy adhesive composition a) and components b) mixed after, the mixture that obtains is used at least one surface, put together in these two surfaces, epoxy adhesive composition between the surface is at about 120 ℃, more preferably from about solidify at least about 10 minutes more than 140 ℃, preferred consolidation was at least about 20 minutes.In preferred scheme, be solidificated in about 200 ℃ or be lower than under 200 ℃ the temperature and carry out.
In this process, the face back epoxy adhesive composition of putting together is solidified and to reach about 4 weeks.
The present invention also relates to utilize two-component epoxy adhesive composition vehicle part to be assembled into the application of the stable assembly of collision.Therefore, the present invention also relates to utilize two-component epoxy adhesive composition to collide the parts of stability assembling (crash-stable assembly).
Embodiment
The component that has provided preparation two-component epoxy adhesive composition of the present invention below a) and components b) embodiment.
Component a)
As a) embodiment of component, component A1 prepares according to following method:
With the acrylonitrile butadiene rubber modified epoxy resin of 14.1 weight % (from the STRUKTOL of Schill+Seilacher company
TM3604 modified epoxies), the liquid-state epoxy resin of 48.6 weight % is (from the D.E.R of Dow Chemical
TM330 Resins, epoxy), the solid epoxy resin of 10.1 weight % is (from the D.E.R of Dow Chemical
TM671 Resins, epoxy), the neodecanoic acid glycidyl ester of 1.5 weight %, the poly-epoxy silane of 1 weight % is (from the SILQUEST of GE Silicones
TMA187) and the toughner of 12.1 weight % (from the RAM of Huntsman company
TM965 toughner) vacuum condition mixed 30 minutes down.After being cooled to 25 ℃, the surface modification silicon-dioxide that adds 6.8 weight % is (from the AEROSIL of Degussa company
TMPyrogenic silica), careful hybrid reaction mixture under vacuum condition.The sealing aliphatic amide that adds 1 weight % at last is (from the ANCAMINE of Air-Products
TM2441 sealing amine) and the dicyanamide of 4.7 weight %, thorough hybrid reaction mixture is about 15 minutes under vacuum condition.Component A2 prepares according to the described method of preparation A1, but is to use the STRUKTOL of 14.0 weight %
TM3604 modified epoxies, 58.2 weight %D.E.R
TM330 Resins, epoxy, the neodecanoic acid glycidyl ester of 1.5 weight %, the SILQUEST of 1.0 weight %
TMA187, the RAM of 12.0 weight %
TM965 toughner, the AEROSIL of 6.8 weight %
TMPyrogenic silica, the ANCAMINE of 1.0 weight %
TMThe dicyanamide of 2441 sealing amine and 5.5 weight %.Component A3 prepares according to the described method of preparation A1, but is to use the STRUKTOL of 13.2 weight %
TM3604 modified epoxies, 54.7 weight %D.E.R
TM330 Resins, epoxy, the neodecanoic acid glycidyl ester of 1.4 weight %, the SILQUEST of 0.9 weight %
TMA187, the RAM of 11.3 weight %
TM965 toughner, the AEROSIL of 6.4 weight %
TMPyrogenic silica, the ANCAMINE of 0.9 weight %
TMThe dicyanamide of 2441 sealing amine and 5.2 weight %.In addition, the calcium oxide that adds 6.0 weight %.Component A4 prepares according to the described method of preparation A1, but is to use the STRUKTOL of 17.0 weight %
TM3604 modified epoxies, the D.E.R of 70.5 weight %
TM330 Resins, epoxy, the neodecanoic acid glycidyl ester of 1.8 weight %, 1.2 weight %, the AEROSIL of 8.3 weight %
TMPyrogenic silica, the ANCAMINE of 1.2 weight %
TM2441 sealing amine.Component A5 prepares according to the described method of preparation A1, but is to use the STRUKTOL of 17.2 weight %
TM3604 modified epoxies, 69.2 weight %D.E.R
TM330 Resins, epoxy, the neodecanoic acid glycidyl ester of 1.7 weight %, 1.0 weight %, the AEROSIL of 5.2 weight %
TMThe dicyanamide of pyrogenic silica and 5.2 weight %.
Components b)
As components b) an example, the B component 1 of bicomponent epoxy adhesive prepares according to following method:
The RAM that under 40 ℃ of vacuum conditions, mixes 57 weight %
TM965 toughner, 4,7 of 20 weight %, 10-three oxygen tridecyls-1,13-diamines, and the diisopropyl naphthalene of 21 weight % 30 minutes.The surface modification silicon-dioxide and the AEROSIL that add 2 weight %
TMBefore the pyrogenic silica, earlier the temperature of mixture is reduced to 25 ℃.Under vacuum condition, mixed this prescription 15 minutes at last.B component 2 prepares according to the described method of preparation B1, but is to use the triisopropyl naphthalene of 21 weight % and the mixture of tetra isopropyl naphthalene to replace the diisopropyl naphthalene.B component 3 prepares according to the described method of preparation B1, but is to use the RAM of 47.1 weight %
TM965 toughner, the dicyanamide of 14.9 weight %, the AEROSIL of 1.6 weight %
TMSilicon-dioxide, 12.0% calcium oxide, the three oxygen tridecyl diamines of 5.4 weight %, and the triisopropyl naphthalene of 17.9 weight % and the mixture of tetra isopropyl naphthalene.B component 4 prepares according to the described method of preparation B1, but is to use the RAM of 44.4 weight %
TM965 toughner, the dicyanamide of 14.8 weight %, the AEROSIL of 1.6 weight %
TMPyrogenic silica, the calcium oxide of 11.3 weight %, the three oxygen tridecyl diamines of 10.0 weight % and the triisopropyl naphthalene of 19.0 weight % and the mixture of tetra isopropyl naphthalene.B component 5 prepares according to the described method of preparation B1, but is to use the RAM of 62.1 weight %
TM965 toughner, 0.9 latent EP 796 promotor (from Huntsman company) of weight % (reference U.S.4 herein, the promotor 2 or 13 in 713,432), 9.6 the aminoethyl piperazine of weight % (aminoethylpiperazine), the LUPASOL of 9.6 weight %
TMPolyvinylamine (from BASF AG), the AEROSIL of 0.8 weight %
TMThe diisopropylnaphthalene of pyrogenic silica and 17.0 weight %.
Viscosity
Component a) and components b) mix after, utilize for 0.01 time Bohlin rheometer (cone (4 °)-dish) swing method to survey its viscosity continuously 23 ℃ and shearing rate.As shown in Figure 1, mixture A5/B5 (weight ratio 2: 1) viscosity increased above 7 hours.As shown in Figures 2 and 3, the viscosity increase of mixture A3/B2 (weight ratio 10: 1) and A4/B4 is respectively above about 30 hours.
In addition, in room temperature and frequency 0.1 to 20s
-1Down, utilize Bohlin rheometer (cone (4 °)-dish) measured component a) and components b) viscosity and the yielding stress of mixing after back 14 days.The Casson model is used to assess viscosity and yielding stress.Table 1 and table 2 have provided mixture A3/B2 and the accordingly result of A4/B4 after 1 hour, 24 hours, 3 days, 8 days and 14 days respectively.Fig. 4 and Fig. 5 have provided A3/B2 and A4/B4 result's curve respectively, wherein, X-coordinate refer to the time (my god), left coordinate refers to viscosity (Pas), right coordinate refers to yielding stress (Pa).
Table 1
Mixture A3/B2 | Viscosity [Pas] | Product stress [Pa] |
1 hour | 188 | 118 |
24 hours | 381 | 69 |
3 days | 427 | 77 |
8 days | 479 | 105 |
14 days | 701 | 115 |
Table 2
Mixture A4/B4 | Viscosity [Pas] | Product stress [Pa] |
1 hour | 190 | 138 |
24 hours | 846 | 164 |
3 days | 960 | 229 |
8 days | 1754 | 289 |
14 days | 5649 | 487 |
The mechanical properties of cured epoxy resin binder composition
Component a) and components b) weight ratio: 10: 1
Component embodiment A 1 a), A2 and A3 respectively with components b) Embodiment B 1 and B2 mix at 10: 1 with weight ratio.Like this, thermal curable epoxy adhesive composition A1/B1, A2/B1 and A3/B2 have just been made.After the described time of table 1 (being called " open hour "), composition is heated to 180 ℃ and kept 30 minutes, forms final curing like this.Measure stretching lap shear strength (the lap shearstrength) and stripping strength (the impact peel strength) (on the steel of steel that oil is arranged and nothing oil, carrying out) respectively according to DINEN 1465 and ISO 11343.
In order to survey the stretching lap shear strength, do substrate with the CRS 1403 (cold-rolled steel) of 1.5mm.
In order to test stripping strength, do substrate with the CRS 140 (cold-rolled steel) of 31.0mm.
The oil of test usefulness is Anticorit 5012S oil.
In addition, utilize the second-order transition temperature of differential scanning calorimetric view (DSC) at 25 ℃-180 ℃ scope build-in test composition A3/B2.
The result is provided by table 3.A3/B2 stretching lap shear strength of testing on the steel that oil is arranged (square expression) and stripping strength (trilateral is represented) are provided by Fig. 6.The A2/B1 that on the oiliness steel, tests stretch lap shear strength (square expression) and stripping strength (rhombus is represented) is provided by Fig. 7.
Table 3
Stretching lap shear strength (on the oily steel) | Open hour before solidifying | A1/B1 [MPa] | A2/B1 [MPa] | A3/B2 [MPa] |
|
21 | 30 | 27 | |
7d | 18 | 27 | 27 | |
14d | 19 | 24 | 28 | |
21d | 19 | 23 | 27 | |
Stripping strength (on the oily steel) | Open hour before solidifying | A1/B1 [N/mm] | A2/B1 [N/mm] | A3/B2 [N/mm] |
|
40 | 30 | 30 | |
7d | 36 | 33 | 27 | |
14d | 33 | 28 | 27 | |
|
28 | 27 | 26 | |
Stripping strength (not having on the oily steel) | Open hour before solidifying | A1/B1 [N/mm] | A2/B1 [N/mm] | A3/B2 [N/mm] |
1d | 42 | 33 | 30 | |
7d | 36 | 33 | 27 | |
14d | 38 | 28 | 27 | |
|
30 | 29 | 26 | |
Second-order transition temperature | 90℃ |
Component a) and components b) weight ratio: 2: 1
Component embodiment A 4 a) respectively with components b) Embodiment B 3 and B4 mix at 2: 1 with weight ratio.Thermal curable epoxy adhesive composition A4/B3 and A4/B4 like this, have just been made.After the described time of table 2 (being called " open hour "), composition is heated to 180 ℃, keeps forming in 30 minutes final curing.Test stretching lap shear strength and stripping strength (carrying out having on oily steel and the no oily steel) respectively according to DIN EN 1465 and ISO 11343.
In order to test the stretching lap shear strength, the CRS 1403 (cold-rolled steel) that uses 1.5mm is as substrate.
In order to test stripping strength, the CRS 140 (cold-rolled steel) that uses 1.0mm is as substrate.
The oil of test usefulness is Anticorit 5012S oil.
In addition, utilize the second-order transition temperature of differential scanning calorimetric view (DSC) at 25 ℃-180 ℃ scope build-in test composition A4/B4.The result is provided by table 4.
Table 4
Stretching lap shear strength (on the oily steel) | Open hour before solidifying | A4/B3[MPa] | A4/B4[MPa] |
1d | 26 | 28 | |
7d | 26 | 28 | |
14d | 26 | 26 | |
|
20 | 26 | |
Stripping strength (having on the oily steel) | Open hour before solidifying | A4/B3[N/mm] | A4/B4[N/mm] |
1d | 26 | 24 | |
7d | 27 | 21 | |
|
25 | 21 | |
|
21 | 21 | |
Stripping strength (not having on the oily steel) | Open hour before solidifying | A4/B3[N/mm] | A4/B4[N/mm] |
1d | 31 | 23 | |
7d | 29 | 19 | |
|
30 | 24 | |
21d | 27 | 25 | |
Second-order transition temperature | 81℃ |
As can be seen, cured epoxy resin binder composition of the present invention has the stretching lap shear strength and the stripping strength that is higher than 20N/mm of 18MPa at least from table 3 and table 4 and Fig. 6 and Fig. 7.There is the stripping strength that records on the oily steel to be comparable to the result who records on the no oily steel.
The stretching lap shear strength of uncured epoxy adhesive composition under the room temperature
In further test, 2: 1 not thermofixation A4/B4 mixture room temperature following 14 days, 21 days and 28 days stretching lap shear strength have been tested.The result is provided by table 5.
Table 5
23 ℃ of storages | Stretching lap shear strength (MPa) |
7d | - |
14d | <0.1 |
21d | 0.2 |
28d | 1.9 |
To top mixture, the test hand pulls intensity after 21 days.
If require early stage washable going property, the stretching lap shear strength can be by using uncle's ammonia, and as 2,4,6-three (dimethylamino methyl) phenol quickens to form as promotor.Table 6 has provided 23 ℃ of stretching lap shear strengths of preserving after 7 days and 14 days of not thermofixation A5/B5 mixture of 2: 1.
Table 6
23 ℃ of storages | Stretching lap shear strength [MPa] |
7d | 7.1 |
14d | 14.6 |
After the induction Procuring, the stretching lap shear of uncured epoxy adhesive composition is strong
Degree
In further testing, the sensed Procuring of above-mentioned mixture.Be applied to mixture in the substrate and assemble, in 10 seconds temperature is risen to 130 ℃ and 140 ℃ respectively from room temperature, and kept at least 30 seconds.
The test result of stretching lap shear strength is provided by table 7.1.5mm CRS 1403 (cold-rolled steel) is as substrate.The oil of test usefulness is Anticorit 5012S oil.
Table 7
The Procuring temperature | The stretching lap shear strength |
130℃ | 0.3 |
140℃ | 1.4 |
Claims (21)
1. two-component epoxy adhesive composition, it comprises:
A) contain first component of first Resins, epoxy and second Resins, epoxy, second Resins, epoxy by elastic body toughening and
B) contain second component of at least a amine compound, this amine compound contains one or more uncle's ammonia and/or parahelium groups at least, and the molecular weight of this amine compound is less than 450g/mol,
Wherein, the ratio of the amine groups sum of amine compound and the epoxide group sum of Resins, epoxy is between 0.01: 1 to 0.5: 1, two components a) and b) mix afterreaction and form the washable composition that goes, described washable thermofixation of going composition to come self collision stable structure tackiness agent.
2. composition according to claim 1, wherein, amine compound is selected from 4,7,10-three oxygen tridecyls-1,13-diamines, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, aminoethyl piperazine, polytrimethylene ether diamines and polytrimethylene ether triamine.
3. according to the described composition of one of aforementioned claim, wherein, two kinds of components a) and b) at least a component contain toughner.
4. composition according to claim 3, wherein, toughner is selected from the compound shown in the formula I
Wherein, m equals 1 or 2, and n is 2-6, R
1For removing the n valency group of the elasticity prepolymer behind end group isonitrile acid fat, amino or the hydroxyl, elasticity prepolymer dissolving or be dispersed in the Resins, epoxy, W and X be respectively-O-or-NR
3-, W and X at least one be-NR
3-, R
2For after removing the phenolic hydroxyl group group and optionally removing amino group, the m+1 valency group of poly-phenol or ammonia phenol, R
3Be H, C
1-C
6Alkyl or phenol, and compound shown in the formula II
Wherein, p equals 1 or 2, and q is 2-6, and Y is-O-,-S-, or-NR
6-, Z is for comprising-OH-NHR
6,-OCN group,
R
4Be the stub of fragment polyethers, polythioester or the polyamine of the stub of hydroxyl, sulfydryl or amino terminated polyether prepolymer or hydroxyl, sulfydryl or amino end capped prepolymer, R
5For the Z group directly is connected in the aromatic carbocyclic on the aromatic nucleus or the p+1 valency group of aromatic hydrocarbon (araliphatic), R
6Be H, C
1-C
6Alkyl or phenyl, and R
7Be methyl or H, or its mixture.
5. according to the described composition of one of aforementioned claim, wherein, the elastomerics of toughness reinforcing second Resins, epoxy is a paracril.
6. according to the described composition of one of aforementioned claim, wherein, two kinds of components a) and b) at least a component comprise latent stiffening agent, its consumption is less than 10% of composition total weight.
7. composition according to claim 6, wherein, latent stiffening agent is a dicyanamide.
8. according to the described composition of one of aforementioned claim, wherein, second components b) contain hydrophobic diluents.
9. according to the described composition of one of aforementioned claim, wherein, two kinds of components a) and b) at least a component comprise one or more additives, it is selected from dive promotor, adhesion promotor, epoxy silane, pyrogenic silica, wetting agent and mineral filler.
10. according to the described composition of one of aforementioned claim, wherein, two kinds of components a) and b) at least a component comprise at least a uncle's list or polyamine or its mixture as promotor, if uncle's list or polyamine be included in component a) in, uncle's list or polyamine are embedded in the polymeric matrix.
11. according to the described composition of one of aforementioned claim, wherein, first component a) and second components b) weight ratio between 2: 1 to 10: 1, the amine groups of amine compound sum and the total ratio of Resins, epoxy epoxide group are between 0.06: 1 to 0.2: 1.
12. according to the described composition of claim 11, wherein,
A) first component comprises first Resins, epoxy of 30 weight %-80 weight %, second Resins, epoxy of 5 weight %-30 weight % and 20 weight % or toughner still less,
B) second component comprises the amine compound of 1 weight %-40 weight %, the hydrophobic diluents of the toughner of 10 weight %-80 weight % and 10 weight %-30 weight %,
And, two kinds of components a) and b) at least a component comprise mineral filler, epoxy silane, wetting agent, pyrogenic silica, the stiffening agent of diving, dive promotor or their mixture.
13. according to one of claim 1-12, mix first component a) and second components b) obtain the washable epoxy adhesive composition that goes.
14. according to one of claim 1-12, mix first component a) and second components b) obtain the washable epoxy adhesive composition that goes, and the mixture that obtains by thermal treatment Procuring.
15. with isolating surface bonding method together, wherein mix according to the component in the described composition of one of claim 1-12 a) and components b), the mixture that obtains is used at least one surface, these faces are linked together, and the epoxy adhesive composition that is clipped between the described surface is solidifying more than 120 ℃.
16. method according to claim 15, wherein, epoxy adhesive composition was solidifying 20 minutes more than 140 ℃ at least.
17. according to claim 15 or 16 described methods, wherein, epoxy adhesive composition puts together after fixing and reached for 4 weeks approximately on the surface.
18. adopt the assembly that connects into collision stability as the described two-component epoxy adhesive composition of one of claim 1-12.
19. be used to connect the purposes of oiliness metallic surface as the described two-component epoxy adhesive composition of one of claim 1-12.
20. be used for vehicle part is connected into the purposes of the assembly of collision stability as the described two-component epoxy adhesive composition of one of claim 1-12.
21. the amine compound that has one or more uncle ammonia and/or a parahelium group causes forming the purposes of washable going property as the reagent of two-component epoxy adhesive composition, the molecular weight of described amine compound is less than 450g/mol.
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EP05004304.1 | 2005-02-28 | ||
EP20050004304 EP1695990A1 (en) | 2005-02-28 | 2005-02-28 | Two-component epoxy adhesive composition |
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CN101128503A true CN101128503A (en) | 2008-02-20 |
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US (3) | US7511097B2 (en) |
EP (2) | EP1695990A1 (en) |
JP (1) | JP4991575B2 (en) |
KR (1) | KR101247047B1 (en) |
CN (1) | CN101128503A (en) |
AT (1) | ATE431837T1 (en) |
BR (1) | BRPI0607978A2 (en) |
CA (1) | CA2599400A1 (en) |
DE (1) | DE602006006907D1 (en) |
ES (1) | ES2323894T3 (en) |
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Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1484797A (en) * | 1976-02-24 | 1977-09-08 | Secr Defence | Epoxide materials |
US4278737A (en) | 1978-08-04 | 1981-07-14 | United States Borax & Chemical Corporation | Anodizing aluminum |
US4476285A (en) * | 1983-03-02 | 1984-10-09 | The United States Of America As Represented By The Secretary Of The Navy | Rubber modified epoxy adhesive |
CA1259897A (en) | 1985-04-02 | 1989-09-26 | Madan M. Bagga | Bonding process using curable epoxide resin adhesive |
US4739019A (en) | 1986-12-08 | 1988-04-19 | Ppg Industries, Inc. | Curable epoxy based compositions having reduced shrinkage during cure |
US4916187A (en) | 1987-02-24 | 1990-04-10 | Ashland Oil, Inc. | Epoxy resin with polyamine-polyphenol solid salt in liquid poly(alkylene oxide) polyamine-polyphenol |
US5278257A (en) | 1987-08-26 | 1994-01-11 | Ciba-Geigy Corporation | Phenol-terminated polyurethane or polyurea(urethane) with epoxy resin |
EP0308664B1 (en) * | 1987-08-26 | 1991-08-28 | Ciba-Geigy Ag | Modified epoxy resins |
DE58909044D1 (en) | 1988-07-28 | 1995-04-06 | Ciba Geigy Ag | Flexibilizer combinations for epoxy resins. |
JPH0343481A (en) | 1989-06-26 | 1991-02-25 | Raytheon Co | Epoxy adhesive |
ZA913801B (en) | 1990-05-21 | 1993-01-27 | Dow Chemical Co | Latent catalysts,cure-inhibited epoxy resin compositions and laminates prepared therefrom |
JP2750217B2 (en) | 1990-11-20 | 1998-05-13 | サンスター技研株式会社 | One-component epoxy adhesive for automotive structures |
DE4318467A1 (en) * | 1993-06-03 | 1994-12-08 | Ruetgerswerke Ag | Diluents for epoxy resin systems |
US5629380A (en) * | 1994-09-19 | 1997-05-13 | Minnesota Mining And Manufacturing Company | Epoxy adhesive composition comprising a calcium salt and mannich base |
AU1520200A (en) | 1998-11-13 | 2000-06-05 | Engelhard Corporation | Catalyst and method for reducing exhaust gas emissions |
DE19858921A1 (en) * | 1998-12-19 | 2000-06-21 | Henkel Teroson Gmbh | Compositions used as structural adhesives contain epoxide-reactive copolymer, reaction product of polyurethane prepolymer with poly:phenol or amino-phenol and epoxy resin |
JP2000239637A (en) * | 1999-02-22 | 2000-09-05 | Toray Ind Inc | Epoxy resin composition for adhesive |
US6248204B1 (en) | 1999-05-14 | 2001-06-19 | Loctite Corporation | Two part, reinforced, room temperature curable thermosetting epoxy resin compositions with improved adhesive strength and fracture toughness |
JP2004508965A (en) * | 2000-06-06 | 2004-03-25 | ダウ グローバル テクノロジーズ インコーポレイティド | Epoxy-based reinforced patch with improved adhesion to oily metal surfaces |
US6572971B2 (en) | 2001-02-26 | 2003-06-03 | Ashland Chemical | Structural modified epoxy adhesive compositions |
AU2002361136A1 (en) | 2001-12-21 | 2003-07-09 | Henkel Teroson Gmbh | Expandable epoxy resin-based systems modified with thermoplastic polymers |
EP1359202A1 (en) | 2002-05-03 | 2003-11-05 | Sika Schweiz AG | Temperature curable epoxy resin composition |
US6645341B1 (en) * | 2002-08-06 | 2003-11-11 | National Starch And Chemical Investment Holding Corporation | Two part epoxide adhesive with improved strength |
US7071263B2 (en) * | 2003-05-19 | 2006-07-04 | 3M Innovative Properties Company | Epoxy adhesives and bonded substrates |
CA2529737C (en) * | 2003-07-07 | 2013-05-07 | Dow Global Technologies Inc. | Adhesive epoxy composition and process for applying it |
ES2276182T5 (en) * | 2004-03-12 | 2015-04-10 | Dow Global Technologies Llc | Epoxy adhesive composition |
EP1602702B2 (en) | 2004-06-01 | 2020-09-16 | Dow Global Technologies LLC | Epoxy adhesive composition |
EP1695990A1 (en) | 2005-02-28 | 2006-08-30 | Dow Global Technologies Inc. | Two-component epoxy adhesive composition |
ATE462762T1 (en) | 2005-06-02 | 2010-04-15 | Dow Global Technologies Inc | IMPACT MODIFIED EPOXY-BASED STRUCTURAL ADHESIVE |
-
2005
- 2005-02-28 EP EP20050004304 patent/EP1695990A1/en not_active Withdrawn
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- 2006-02-28 ES ES06721115T patent/ES2323894T3/en active Active
- 2006-02-28 EP EP20060721115 patent/EP1885764B1/en active Active
- 2006-02-28 KR KR1020077019536A patent/KR101247047B1/en active IP Right Grant
- 2006-02-28 BR BRPI0607978-4A patent/BRPI0607978A2/en not_active Application Discontinuation
- 2006-02-28 WO PCT/US2006/007053 patent/WO2006093949A1/en active Application Filing
- 2006-02-28 CA CA 2599400 patent/CA2599400A1/en not_active Abandoned
- 2006-02-28 AT AT06721115T patent/ATE431837T1/en not_active IP Right Cessation
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- 2006-02-28 DE DE200660006907 patent/DE602006006907D1/en active Active
- 2006-02-28 US US11/363,692 patent/US7511097B2/en active Active
- 2006-02-28 CN CNA2006800063381A patent/CN101128503A/en active Pending
-
2008
- 2008-10-16 US US12/252,521 patent/US7834091B2/en not_active Expired - Fee Related
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CN102575138A (en) * | 2009-09-11 | 2012-07-11 | 3M创新有限公司 | Curable and cured adhesive compositions |
CN102575138B (en) * | 2009-09-11 | 2013-10-16 | 3M创新有限公司 | Curable and cured adhesive compositions |
CN103387807A (en) * | 2012-05-10 | 2013-11-13 | 株式會社海廣 | Epoxy resin adhesive composition and clean room perforated floor panel comprising the same |
CN106753143A (en) * | 2016-12-21 | 2017-05-31 | 南京诺邦新材料有限公司 | A kind of low-temperature setting underfill with heat conduction function and preparation method thereof |
CN108300389A (en) * | 2017-01-13 | 2018-07-20 | 杭州之江有机硅化工有限公司 | A kind of epoxy adhesive composition and preparation method thereof and application |
CN108300389B (en) * | 2017-01-13 | 2019-03-12 | 杭州之江有机硅化工有限公司 | A kind of epoxy adhesive composition and preparation method thereof and application |
CN114096583A (en) * | 2019-07-09 | 2022-02-25 | 汉高股份有限及两合公司 | Two-component (2K) compositions based on modified epoxy resins |
CN115637124A (en) * | 2021-07-19 | 2023-01-24 | 沃顿科技股份有限公司 | Preparation method of bi-component epoxy resin adhesive and bi-component epoxy resin adhesive prepared by same |
CN115637124B (en) * | 2021-07-19 | 2023-09-22 | 沃顿科技股份有限公司 | Preparation method of bi-component epoxy resin adhesive and bi-component epoxy resin adhesive prepared by same |
Also Published As
Publication number | Publication date |
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JP2008531817A (en) | 2008-08-14 |
US20110020652A1 (en) | 2011-01-27 |
KR101247047B1 (en) | 2013-03-25 |
EP1885764B1 (en) | 2009-05-20 |
JP4991575B2 (en) | 2012-08-01 |
ATE431837T1 (en) | 2009-06-15 |
CA2599400A1 (en) | 2006-09-08 |
EP1885764A1 (en) | 2008-02-13 |
US7834091B2 (en) | 2010-11-16 |
WO2006093949A9 (en) | 2006-11-09 |
US20060205897A1 (en) | 2006-09-14 |
US7511097B2 (en) | 2009-03-31 |
BRPI0607978A2 (en) | 2009-10-27 |
ES2323894T3 (en) | 2009-07-27 |
US7951456B2 (en) | 2011-05-31 |
EP1695990A1 (en) | 2006-08-30 |
US20090065143A1 (en) | 2009-03-12 |
DE602006006907D1 (en) | 2009-07-02 |
KR20070106534A (en) | 2007-11-01 |
WO2006093949A1 (en) | 2006-09-08 |
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